Composition and method for permanent waving of hair on the human head



United States Patent O COMPOSITION AND METHOD FOR PERMANENT WAVING OF HAIR ON THE HUMAN HEAD Milton H. Schwarz, Morristown, N. J., and Gerald Orgel,

Bronx County, N. Y., assignors to Turner Hall Corporation, New York, N. Y., a corporation of New York No Drawing. Application July 23, 1953, Serial No. 369,964

13 Claims. (Cl. 167-871) This invention relates to permanent waving of hair on the human head.

In its preferred form, our invention pertains to that type of permanent waving, commonly known as cold waving, wherein the hair is treated with a softening composition containing a disulfide disrupting agent as, for example, a mercaptan or a sulfite which converts the disulfide groups of the hair keratin, and more particularly of the hair cystine, into sulfhydryl groups. The hair is shaped, for example by winding on rods, before or after the softening step. Thereafter, the disulfide bonds are substantially restored by a setting treatment so that the finished hair will have approximately its original elasticity and, accordingly, will retain its altered shape.

At present, powerful oxidants such as hydrogen peroxide, sodium bromate, sodium chlorate and sodium chlorite are employed to restore the disulfide bonds. It is recognized that the use of such oxidants is accompanied by deleterious side effects such, for instance, as porosity, embrittlernent, harshening and, under certain conditions, lightening of color. It is believed that some of these effects are due to over-oxidation of the cysteine, that is to say, oxidation beyond the cystine stage.

A further complication in the use of these powerful oxidants is the selection of a proper concentration. If the concentration is low enough to avoid deleterious side effects, the re-oxidation of the cysteine may be insuficient, particularly deep within the hair strands. But if a concentration is used which is sufficiently high to insure reformation of the disulfide bond deep within the hair strand, oxidation of the cysteine, at least near the surface of the strand, will be carried too far.

It has been determined by analysis that all the cystine content of the hair is not restored as such after disulfide bond breakdown and subsequent re-oxidation in presentday commercial permanent hair waving with the powerful oxidants now used. The actual percentage of recovery is a balance between failure to re-oxidize some cysteine deep in the hair strands and over-oxidation of other cysteine near the surface of the strands. The recovery obtained commercially is considered acceptable for permanency of waving but leaves much to be desired insofar as texture and strength of hair are concerned.

It is the salient object of our invention to provide a method and setting compositions for re-oxidizing softened hair which are not subject to the foregoing drawbacks.

It is another object of our invention to provide a method and compositions of the character described for controlled oxidation of reduced keratin of hair on the human head whereby only the original state of oxidation of the hair is attained and no higher states.

It is a further object of our invention to provide a method and compositions of the character described which will restore substantially more of the original cysteine than is recovered at present and will, accordingly, leave the hair in a state far closer to its original condition, except for shape.

It is an additional object of our invention to provide ice ' powerful oxidant that may be present and release this potential slowly and at the proper energy level for converting cysteine to cystine but no more.

It is yet another object of our invention to provide a method and compositions of the character described which are sensitive to even low concentrations of any powerful oxidants that may be present so as thereby to ensure complete re-oxidation of all the cysteine.

It is yet a further object of our invention to provide compositions of the character described which are inexpensive to manufacture.

It is still another object of our invention to provide a method of the character described which is similar to present methods in its manipulative steps so that additional skill is not required to practice the same.

Other objects of our invention in part will be obvious and in part will be pointed out hereinafter.

Our invention accordingly consists in the compositions and steps which will be exemplified in the compounds and processes hereinafter described and of which the scope of application will be indicated in the appended claims.

Pursuant to our invention the restoration of the cystine is accomplished by setting softened hair with dehydroascorbic acid in water.

We have discovered that dehydroascorbic acid has the specific capacity to convert cysteine to cystine in hair on the human head, that is, to oxidize such cysteine to cystine but not to carrythe oxidation to a more advanced stage. Hence, as a dehydroascorbic acid setting solution penetrates a softened hair strand it will reconvert the sulfhydryl groups back to disulfide groups. Further exposure of the disulfide groups to said oxidant will not result in the formation, for example, of cysteic acid or inorganic sulfates.

We have determined that dehydroascorbic acid is effective for the foregoing purpose over a pH range varying from 2 to 10 although at the extreme alkaline end of said range it has a marked tendency to decompose and, therefore, is difficult to employ. The best results are secured at a pH of 7.4 but from a pH of 2.2 to a pH of 8 good results are obtained, the preferred range being from 5 to 8 when dehydroascorbic acid is the only oxidant present. Insofar as hair conditioning is concerned, the peak performance is 7.4, but results at this pH are not markedly superior to results secured anywhere within the preferred range.

Dehydroascorbic acid will function in accordance with our invention at concentrations as low as 0.03 percent by weight of the setting solution. However, increasingly better results are obtained as the concentration of dehydroascorbic acid increases up to about 0.5 percent and setting is satisfactory at a concentration as highas 0.8 percent.

It is best to employ a substantial concentration of dohydroascorbic acid, e. g. 0.5 percent, inasmuch as dehydroascorbic acid tends to be unstable in water at a pH over 5, being particularly unstable at any pI-I well within the alkaline range, and inasmuch as during reoxidation of the softened hair the dehydroascorbic acid converts to ascorbic acid which is not effective for re-hardening (setting) of the hair.

A typical oxidizing solution for neutralizing, that is to say, setting, hair which has been softened by treatment with a disulfide reducing agent is one gram of dehydroascorbic acid, 8.3 grams of disodium hydrogen phosphate and 1.2 grams of anhydrous citric acid to a pint of water, the pH being adjusted to 7.0. This setting solution is rinsed through the hair for approximately six minutes and leaves the hair permanently waved and with a soft and silky texturazthezhain strands being strong and-nonporous and having their original color.

In accordance with a feature of the present invention the dehydroascorbic acid can be formed in situ. This may .be effected by. providing. ascorbic. acid. together With an .active oxidizingreagent, i. .e.l. an..oxidizi ng reagent of sufficient strengthto.oxidizeascorbic acid-. to dehydroascorbic acid. The dehydroascorbichacid functions to oxidize cysteine to cystine. and in..so.doing..reverts.to ascorbic :acidthus completing a 'closed'cycle. Typical active oxidizingreagents of sufiicient strength arexthose Which conventionally are. used for. neutralizing hair,.such, for example, as hydrogen peroxide, sodiumfbromate, sodium chlorate, sodium .chlorite and. sodium. .perborate.

: Theascorbic acidwill. convert to dehydroascorbic acid and .the dehydroascorbic acid will functionpursuant to my invention to set softened hair anywhere. within the pH rangementionedabove, i.- e. .from 2 to. 10. .However, some-f the active oxidizingreagents work bestwithin more limited ranges, and under theseconditions. it will be understood thatthe pH of the settingsolutiotrwill be governed by the oxidizing reagent employed. Thus,.with hydrogen peroxide the preferred pH is about 2.2;with sodium bromate and sodium chlorate thepreferred-pI-I is from 5.5 to 6.2; and with sodium chlorite. the preferred pH is about 9.2. At all of these pH values ascorbic acid is oxidized by the .active oxidizing reagent to dehydroascorbic acid and the dehydroascorbic acid effectively .oxides cysteine to cystine. We-desirably do not use the highest values of. pl-Linasmuch as, under suchcircumstances, the setting solution is irritating to the scalp and the dehydroascorbic acid tends to-form.:inactive.compounds and, therefore, does not. reconvert completely to ascorbic acid so as to be ready for re-use inthe closed cycle.

Theconcentration of ascorbicacid may vary from 0.03 to 0.5 percent,.the preferred concentration being 0.05 percent. by weight. It'may be mentioned that in the equilibrium which is reached in the conversion of ascorbic vacid to dehydroascorbic acid and baclcto ascorbic .acid the amount of dehydroascorbic acid present at any..given time isa function of the concentration of ascorbic acid, the-pH of the setting composition and the concentration and the constitution of the active oxidizing reagent. Hence, it is desirable to adjust these values to obtain an .optimum amount of dehydroascorbic acid withany specificactive oxidizing reagent. However, rthe results.obtained are not, markedly afTected-bysmall changes inthe concentrations of the active oxidizing'reagent' and ascorbic acid so thatthese may vary over a wide range. For example, satisfactory results are. obtained withascorbic acid varying from 0.03 to 0.25. percentby Weight. The active oxidizing reagent can vary almost at willproviding that, as is well known; said reagent is .not. present in .such quantity as to deleteriously affect. the. hair, or. scalp, e..g. to bleach the hair.

Set forth below-are typical examples of different setting solutions utilizing ascorbic .acid and ,anactivemxidizing reagent.

/v gram ascorbic acid 2 oz. 20 vol. hydrogen peroxide 4 grams citric acid Q. s. a :pint with water 3.5 grams acetic acid 0.6.gram sodium acetate .Q., s..- a pint with water -,Adjus t pHto 3.7

Mggram ascorbic acid .2.oz.-;-20vol.: hydrogen peroxide 83 grams disodium hydrogen phosphate 1.2 grams citric acid Q. s. a pint with water Adjust pH to 7 1 gram ascorbic acid 28 grams potassium bromate 1 gramv disodium. hydrogen phosphate Q. s. a quart with Water Adjust pH to 5.5

Hair treated first with. a;softening solution andJthen with a setting-solution embodying thepresent-invention is far softer, has a much. better hand and isstronger, less porous and less brittle than cold waved hair which has been set with present-day commercial powerful oxidants. The improved effects are most=marked when dehydroascorbic acid is used alone but are quite noticeable even when the dehydroascorbic acid is produced in. situ. by oxidation of ascorbic acid.

By way of example and Without in. any way'limiting the scope of our invention, a typical hair Waving process incorporating the present invention is set forth below.

A head of hair is blocked off and wetted by atypical softening composition as, for instance, a water solution of ammonium thioglycollate at a pH of 9.2 and a concentration of 7% by weight. The wet tresses are wound on curlers and re-wetted with the softening composition. After the hair has softened lukewarm water is rinsed therethrough. Nowthere is rinsed throughthe hair a setting solution embodying our invention as, for example, the solution given in Example I. The rinsingis carried on for approximately four minutes. The hair thenxcan be unwound from the curlers; and, if desired, the'setting solution applied to each curl.

Attention is called to the fact that if an unduly high percentage of a powerful oxidant is employed it will not deleteriously affect the hair inasmuch as the ascorbic acid tends to absorb the excess oxidizing potential of such oxidant and thereby ameliorates any adverse, effects. Conversely, if the amount of. the active oxidizing reagent is quite small, although enough stoichiometrically .to complete the reaction, the solution nevertheless will .function for setting inasmuch as ascorbic acid is quitesensitive to active oxidizing reagents and, therefore, willinsure the complete re-setting of previously softenedhair. It .is. for these reasons that the amount of active oxidizingreagent can be variel so widely.

It will be observed that the concentration of ascorbic acid with which suitable results can be obtained isquite small. It must, however, be remembered that the ascorbic acid constantly is being converted to dehydroascorbic acid so that the supply of dehydroascorbic acid constantly is being replenished; and it is not necessary, accordingly, to practice the invention with the same-high concentration of dehydroascorbic acid as is employed when dehydroascorbic acid is utilized by itself, that is to say, not in conjunctionwith an active oxidizing reagent.

It will be understood that when any sodium salt is mentioned orclaimed herein the corresponding potassium salt can be substituted in its place and vice versa.

It'thus will be seen that there are. providedcompositions and processes which achieve all the objects of the invention' and are well adapted to meet the-.conditions of practical use.

As various possible embodiments .mighttbe' madeof the above invention, and as various,;changes might be made in the embodiment above set .forth, it :is to be understood that all matter 'hereinidescribed 'isxtogbe interpreted as illustrative and not rina. limiting sense.

Having thus described our. invention, -wepclaim.as;new

zafid 'desire'to secure by..Letters Patent:

..1. .A.-setting: compositionxadapted; tor-.be.'used:subsequently .toJa previously applied compositioncfor disrupting the human head and after said disrupting composition has been substantially removed: said setting composition comprising an aqueous carrier and dehydroascorbic acid at a pH range between 2 and 10, and a concentration between 0.03 percent and 0.8 percent by weight, said setting composition being free of a disulfide reducing agent.

2. A setting composition adapted to be used subsequently to a previously applied composition for disrupting disulfide bonds of cystine in permanently waving hair on the human head and after said disrupting composition has been substantially removed: said setting composition comprising an aqueous carrier and dehydroascorbic acid at a pH range between 2 and 10, and a concentration of about 0.05 percent, said setting composition being free of a disulfide reducing agent.

3. A setting composition adapted to be used subsequently to a previously applied composition for disrupting disulfide bonds of cystine in permanently waving hair on the human head and after said disrupting composition has been substantially removed: said setting composition comprising an aqueous carrier and dehydroascorbic acid at a pH range between 5 and 8, and a concentration of about 0.05 percent, said setting composition being free of a disulfide reducing agent.

4. A setting composition adapted to be used subsequently to a previously applied composition for disrupting disulfide bonds of cystine in permanently waving hair on the human head and after said disrupting composition has been substantially removed: said setting composition comprising an aqueous carrier, ascorbic acid and at least one active oxidizing reducing agent selected from the group consisting of hydrogen peroxide, sodium and potassium bromate, chlorate and chlorite, said setting composition being free of a disulfide reducing agent.

5. A setting composition adapted to be used subsequently to a previously applied composition for disrupting disulfide bonds of cystine in permanently Waving hair on the human head and after said disrupting composition has been substantially removed: said setting composition comprising an aqueous carrier, ascorbic acid and an active oxidizing reagent, the concentration of ascorbic acid being between 0.03 and 0.25 percent by Weight, said setting composition being free of a disulfide reducing agent.

6. A setting composition adapted to be used subsequently to a previously applied composition for disrupting disulfide bonds of cystine in permanently waving hair on the human head and after said disrupting composition has been substantially removed: said setting composition comprising an aqueous carrier, ascorbic acid and an active oxidizing reagent, the pH of said composition being between 2 and and the concentration of the ascorbic acid being between 0.03 and 0.25 percent by Weight, said setting composition being free of a disulfide reducing agent.

7. A setting composition adapted to be used subsequently to a previously applied composition for disrupting disulfide bonds of cystine in permanently waving hair on the human head and after said disrupting composition has been substantially removed: said setting composition principally comprising an aqueous carrier, ascorbic acid, an active oxidizing reagent and an acidifying reagent to impart a pH to the composition between 2 and 10, the concentration of the ascorbic acid being between 0.03

and 0.25 percent by weight, said setting composition being free of a disulfide reducing agent.

8. In a method of permanently Waving hair on the human head in which the hair is shaped and treated with a softening composition for disrupting disulfide bonds of cystine: that improvement comprising the steps of subsequently substantially restoring the softened hair to its original condition by applying to the softened hair a setting composition comprising an aqueous carrier and dehydroascorbic acid.

9. In a method of permanently waving hair on the human head in which the hair is shaped and treated with a softening composition for disrupting disulfide bonds of cystine: that improvement comprising the steps of subsequently substantially restoring the softened hair to its original condition by applying to the softened hair a setting composition comprising an aqueous carrier and dehydroascorbic acid at a pH range between 2 and 10.

10. In a method of permanently waving hair on the human head in which the hair is shaped and treated with a softening composition for disrupting disulfide bonds of cystine: that improvement comprising the steps of subsequently substantially restoring the softened hair to its original condition by applying to the softened hair a setting composition comprising an aqueous carrier and dehydroascorbic acid at a pH range between 2 and 10, and a concentration between 0.03 percent and 0.8 percent by Weight.

11. In a method of permanently waving hair on the human head in which the hair is shaped and treated with a softening composition for disrupting disulfide bonds of cystine: that improvement comprising the step of subsequently substantially restoring the softened hair to its original condition by applying to the softened hair a setting composition comprising an aqueous carrier, ascorbic acid and an active oxidizing agent.

12. In a method of permanently Waving hair on the human head in which the hair is shaped and treated with a softening composition for disrupting disulfide bonds of cystine: that improvement comprising the step of subsequently substantially restoring the softened hair to its original condition by applying to the softened hair a composition containing dehydroascorbic acid.

13. In a method of permanently waving hair on the human head in which the hair is shaped and treated with a softening composition for disrupting disulfide bonds of cystine: that improvement comprising the step of subsequently substantially restoring the softened hair to its original condition by applying to the softened hair dehydroascorbic acid formed in situ on the hair.

References Cited in the file of this patent UNITED STATES PATENTS 2,540,980 Den Beste a- Feb. 6, 1951 2,600,624 Del Zoppo June 17, 1952 FOREIGN PATENTS 931,447 France Feb. 23, 1948 I 270,698 Switzerland Dec. 1, 1950 OTHER REFERENCES Merck Index, 6th ed., 1952, page 310, entry Dehydroascorbic Acid.

Annual Review of Biochem, vol. III, 1934, page 273, ibid., vol. XIV, 1945, pp. 7, 8 and 470. 

1. A SETTING COMPOSITION ADAPTED TO BE USED SUBSEQUENTITY TO A PREVIOUSLY APPLIED COMPOSITION FOR DISRUPTING DISULFIDE BONDS OF CYSTINE IN PERMANENTLY WAVING HAIR ON THE HUMAN AND AFTER SAID DISRUPTING COMPOSITION HAS BEEN SUBSTANTIALLY REMOVED: SAID SETTING COMPOSITION COMPRISING AN AQUEOUS CARRIER AND DEHYDROASCORBIC ACID AT A PH RANGE BETWEEN 2 AND 10, AND A CONCENTRATION BETWEEN 0.03 PERCENT AND 0.8 PERCENT BY WEIGHT, SAID SETTING COMPOSITION BEING FREE OF A DISULFIDE REDUCING AGENT. 